Mr Doyle, who is currently Deputy Head of the EU Service for the Foreign Policy Instruments Unit, previously served as a crisis response planner and in the European Agency for Reconstruction in Kosovo.
He takes over from Ambassador Hans Duynhouwer, who told journalists last week he would be leaving the country following a four-year stint as Ambassador and Head of the Delegation of the European Union in Lesotho.
Meanwhile, Ashton on Friday also announced the appointment of new Heads of EU Delegations to Eritrea, and Madagascar.
Christian Manahl has also been appointed Head of the EU Delegation to Eritrea. Previously an Austrian diplomat, Manahl joined the Commission in 1996 and has done a variety of Africa-related foreign policy jobs in Brussels and in Delegation, as well as secondments to the UN in the Democratic Republic of Congo and Somalia.
At the moment, he is political counselor at the EU Delegation in South Sudan.
Ashton also said Antonio Sanchez-Benedito Gaspar would be the new head of the EU delegation to Madagascar. An experienced national diplomat, Gaspar served in a variety of policy jobs in Madrid on Africa and Latin America before becoming Ambassador to Ethiopia (2008-2011) and currently Ambassador at Large for the Sahel.
Ashton said in a statement: “Their talent and expertise are significant assets for the EU’s external action and I look forward to working with them in their new roles.”